Cellulose organic ester composition of matter containing a benzyl ether of diethylene glycol



Patented May 8, 1934 oELLULosE ORGANIC ESTER COMPOSITIO F MATTER CONTAINING A BENZYL ETHER 0F DIETHYLENE GLYOOL Stewart J. Carroll, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation oi New York No Drawing. Application June 19, 1931, Serial No. 545,630

claims. (Cl. 106-40) This invention relates to compositions of matency, toughness and other properties which will ter in which cellulose organic esters, such as enhance the value of the resulting product. cellulose acetate, are combined or mixed with Addition products for the same or similar purother substances, such as a compatible plasticizer, poses are also added to cellulose acetate to pre- 5 with or without a common solvent for both, and pare it for use'in the other plastic arts, such as in so with or without other useful addition asentss the manufacture of lacquers, varnishes, artificial that the resulting product will have properties silk filaments, molded compounds and the like. such as will make the composition highly ad'- While the plasticizers or other addition agents vantageous for use in the plasticand-analogous heretofore discovered have had their utility in arts, such, for instance, as the manufacture of the art, the increasing use to which cellulose ace 5 pp Sheets tissue, photographic film, tate has been put and the increasing number of melding comD and products, tific al S desirable properties required of cellulose acetate varnishes or lacquers, coating compositions and for most purposes have made the discovery of the like.- new and economical plasticizers or other addi- .1'5 This application is in part a continuation of my tion agents a matter of considerable importance 7 application Serial No. 389,450, filed August 30, to the art. This has been a problem of some 1929. V v difficulty, since many of the nitrocellulose solv- One object of this invention is to produce a ents are not solvents for cellulose acetate, and composition of matter which may be made into many substances which act as plasticizers for permanently, transparent, strong and fiexible nitrocellulose are not sufficiently compatible with 7 sheets or films of desired thinness which are subcellulose acetate to be used as plasticizers in stantially waterproof, are unaffected by ordinary cellulose acetate compositions.

photographiofluids and possess the desired prop- I have discovered that valuable properties may erties of a support for sensitive photographic be induced in and/or contributed to compositions '25 coatings. Another object of my invention is to containing organic esters of cellulose, such as cel- 80 produce a composition of matter'which is capable luloseacetate, by adding thereto as a plasticizing of easy and convenient manipulation in the compound a benzyl ether of diethylene glycol, plastic and analogous arts, such as in the manunamely the monobenzyl ether of diethylene glycol facture of sheets, films; artificial silk filaments, or the dibenzyl ether of diethylene glycol. These 3'0 varnishes, lacquers and the like, and to produce ethers have the formulae S5 tions which can-be molded at elevated temperaa composition which will not injure, or-be inr lured. by, the'substances'or surfaces with which f it is associated during manufacture. Another and i my inventmn is produce comp? Cal-I5.CHz;O.CH2.CH2.O.CH2.CHz.O CI-IzCsHs tures and high pressures to produce plastic prodrespect v y- The benzyl ether of diethylene ucts having the desirable properties of celluloid. glycol is frequently referred to as ,Bf3'-dibenzoxy Still another object of my invention is to produce ethyl ether. The particularly useful properties a-C mD i n (if-m tter containing cellulose aoe- .which they induce in or contribute to cellulosic '3 40 tate which has a h degree O fl y, 0 compositions containing them are hereinafter nes's; pliability and clarity. Qther objects will enumerated,

become apparent to those skilled in the a to The monobenzyl ether of diethylene glycol may Whlch this lnventlon pertams- U be prepared as follows: 184 g. of sodium is dis- -Whilc cellulose acetate has been known for decsclvedl in 35 kg. of diethylene glycoL The Sodium '45 ades, it has also been known-thatto utilize it'in dissolves Slawly at mom temperature but Very o r due- 50 agents are also added for the purpose f e off, and the filtrate fractionated under reduced vamus Plastic arts it f to idly at 100 0. To this solution is added 1 kg of with such plasticizing or con itioning agen s as benz L O yl chlol 1de. Themixtureis heated at 100-120 tnphenyl phosphate monochlomaphthalene or C. for four hours and allowed to stand over night.

the like. Certain of these and other additlon T precipitated Sodium chloride is then filtered ing the inflammability of the product. Plastic inducingagents, h as t higher alcohols and pressure through aneflicient column. After two theirestersare sometimes also added- Similarfractionations, the monobenzyl ether of et y- 1y, addition compounds of various kinds ha e lene glycol is obtained as a colorless liquid boiling 5 been employed to. increase flexibility, transparat 176-179" C. under 18 mm. pressure.

The dibenzyl ether of diethylene glycol may be prepared in the following manner: 184 g. of sodium is dissolved in 3.5 kg. of diethylene glycol monobenzyl ether. The sodium dissolves slowly at room temperature but more rapidly .as the temperature is raised. 1 kg. of benzylchloride is then added and the solution warmedoman oil bath at 100-120 C. for several hours. Benzene is added and the solution is filtered to remove the sodium chloride. After removal. of .the benzene by distillation, the filtrate is distilled under reduced pressure. The dibenzyl ether of diethylene glycol distills over at 226-238 C. under 15 mm. pressure.

In order that those skilled in this art may better understand my invention, I would state, by way of illustration, that for. the manufacture of photographic film or other sheets my'new composition of matter may be compounded as follows: 100 parts of acetone-soluble cellulose acetate, i. e. cellulose acetate containing from 36% to 42% acetyl radical, approximately, is dissolved with stirring at atmospheric tempera.- ture in 300 to 500 parts, preferably 400 parts, by weight of acetone. To this solution may be added from 10 to 50 parts by weight of the monoor the di-benzyl ether of diethylene glycol, it being found preferable to employ approximately 50 parts thereof. Within the limits stated, the amount of plasticizer may be decreased or increased, depending upon whether it is desired to decrease or increase, respectively, the properties which these plasticizers contribute to the finished product. The amount of solvent employed may also be increased or decreased, depending upon Whether it is desired to have a more or less freely flowing composition, respectively.

A composition of matter prepared as above described may be deposited upon any suitable film-forming surface to form a film or sheet,- in a manner well known to those skilled inthe art. A film so produced has permanently brilliant transparency (even where as much as ,50 to parts of benzyl ether of diethylene glycol per 100 parts of cellulose organic ester, such as cellulose acetate, is used) and low infiammability, burning no more readily than ordinary newsprint. Films or sheets produced in accordance with my invention are quite tough and flexible. For instance, films of cellulose acetate .plasticized with 10% to 50% (parts by weight based on the acetate) of the dibenzyl ether of diethylene glycol had an initial flexibility of from 50% to 250% greater than that of film containing no plasticizer, and cellulose acetate films plasticized with 10% to 50% of the monobenzyl ether-of diethylene glycol had an initialfiexibility of from 50% to 1250% greater than that of film plasticized with 18% of monochlornaphthalene. Furthermore, film so plasticized maintains flexibility in a superior fashion. For instance, films containing 30% and 50% of the dibenzyl ether of diethylene glycol maintained flexibility at C. for 130 days and 365 days, respectively, whereas an unplasticized film became brittle in 30 days. A film containing 20% of the monobenzyl ether of diethylene glycol maintained flexibility at 65 C. for 72 days, whereas an unplasticized film became brittle in 30'days. This demonstrates that films so plasticizedwill-withstand ordinary usage satisfactorily-for many years. The sum total of the above advantageous properties of products produced from my new compositions is considerably inexcess-of that of .verted into: a hard Y translucent products produced with what have previously been regarded as the better plasticizers.

Other similar solvents (instead of acetones) which are compatible with the cellulose acetate and my new plasticizers may also'occur to those skilled in this art. In like manner these plasticizers may be compounded with other single organic esters of cellulose, such as cellulose pro- :pionate, butyrate and the like, or with mixed organicand/or inorganic esters, such as cellulose aceto-stearate, cellulose aceto-propionate, cellulose aceto-malategor cellulose nitro-acetate, a suitable solvent which Wlill dissolve both the cellulosic derivative and the plasticizer being employed.

be employed for 'wet spinning. It may be .de-'

sired to employ compositions. of different viscosity or evaporation characteristics, but. :thisis a mere matter of changing the solvent proportion oradding evaporation retardentsioriother high or intermediate boiling constituents, ashas been well known in the art for more. than at.-decade. My novel plasticizers may also beemployed with advantage in connection with a number .of the known lacquer and varnish formulae with which they may be found ;to be compatible. In such cases the plasticizer isusually :fir-st put .into solution in the cellulose derivative solution,and .if non-solvents are added forwthe. purposeof cheapening the composition they arezadded. only .to such an extent-as will not precipitate the derivative from solution. usually. employed in larger amounts, such as from 50 to 60 parts, in compounding lacquers. Other uses within the scope of my invention will-.also suggest themselvesto those skilled in the art and are to be included Within the scope. of .the .claims appended hereto.

The benzyl ethers of diethylene glycol may also beadvantageously used as plasticizers in cellulose acetate molding compositions. For. instance, .when about-30% (parts by weightsbased onxthe celluloseacetate) of the mono-pr the di-benzyl etherof diethylene g-lycolis homogeneously mixed with cellulose acetate, the mixture maybe conplastic product bymolding at a temperature of 140- to 160 C. and .a

pressure of about 2500 pounds per square inch for a period of from 2 to 5 minutes, in amannenalready known to those skilled in molding compounds of that nature. i

Moreover, I have foundthat, upon the-addition to celluloseacetate of approximately 100% of the monobenzyl or the dibenzyl-ether of'diethylene .gl-ycol, quiteunexpected compatibilityof the plasticizer with the cellulose acetate exists and also that quite unexpected flexibility, plasticityand clarity of the final product results. Contrary :to

experience in most cases Where such a large-proportion of plasticizer is used, nosweating-out-or crystallizingout-of the plasticizer occurs. :Such compositions: have j great. utility where-a :highly flexible compound is desired, such as-in the coating of a base (forinstance, cloith'or other-fabric) in the productionof relatively thin-sheets wherein more thanrthe usual .flexibility' is important.

Also. the plasticizer is Such a composition, if converted, for instance, into sheet form will be found to be supple and non-rigid, and to have the ability to conform readily to a surface upon which it may be placed, and this even at atmospheric temperatures.

These novel compositions of matter are produced by merely mixing the plasticizer with cellulose acetate and then adding sufiicient of a common solvent, such as acetone, whereupon an intimate mixture of the plasticizer with the cellulose acetate results. The amount of acetone or other common solvent to be employed varies, of course, within rather wide limits depending upon the fluidity of the composition desired. 100 parts of acetone will suifice for many purposes, although we prefer to use 400 parts. Various high boilers or evaporation retardents, such as ethyl lactate, amyl acetate or the like may also be added if desired, as is well known in this art.

The composition of matter so produced may then be coated into sheets in the usual way by depositing it upon plates or rolls and permitting the solvent to evaporate. If my novel composition is to be employed in the manufacture of artificial leather, it may be coated upon, for instance, a cloth support and the solvent permitted to evaporate, or the cloth support may be caused to pass through the cellulose acetate-plasticizer composition and permitted to absorb the solution, the solvent in the coating being then permitted to evaporate. In either case, the solvent may, of course, be recovered if desired by condensing the vapors etc.

While above and in certain of the claims appended hereto, I have referred to the use of a plasticizer in approximately equal proportions, namely in a ratio of approximately 100%, it will be understood that within this terminology variations of from 10 to 15% less than 100% of plasticizer and as much as 25 to 50% more than 100% of the plasticizer may in some instances be desirable.

What I claim as my invention and desire to be secured by Letters Patent of the United States is:

1. A composition of matter comprising an organic ester of cellulose and the dibenzyl ether of diethylene glycol.

2. A composition of matter comprising cellulose acetate and the dibenzyl ether of diethylene glycol.

3. A composition of matter comprising 100 parts of cellulose acetate and about 10 to 100 parts, by weight of the dibenzyl ether of diethylene glycol.

4. A relatively thin sheet comprising 100 parts of cellulose acetate and about 10 to 100 parts, by weight of the dibenzyl ether of diethylene glycol.

5. A molding composition adapted to molding under elevated temperatures and high pressures, comprising 100 parts of cellulose acetate and approximately 15 to 50 parts by weight, of the dibenzyl ether of diethylene glycol.

STEWART J. CARROLL. 

